Fire extinguishing foam concentrate comprising an organic fluorine compound and a solubilizing agent

ABSTRACT

A water containing fire extinguishing foam concentrate comprises an active ingredient about 1% to 10% by weight of a compound of the general formula WHEREIN A IS A NUMBER OF BETWEEN ONE AND THREE INCLUSIVE, X is hydrogen or Y and Y is a hydrophilating group such as polyethyleneglykol or an aminoxyd or ammoniumsalt containing group. The concentrate may also contain solubilizing agents.

United States Patent Rossmy et al. Apr. 11, 1972 154] FIRE EXTINGUISHING FOAM 3,257,407 6/1966 Brace ..252/357 CONCENTR ATE COMPRISING AN 3,258,423 6/1966 Tuve et aL... ..252/3 3,274,244 9 1966 Mackenzie ..260/561 fifi igg g gg gg AND 3,418,352 12/1968 Rossmy et al.... .....260/448.8 A SOL 3,472,894 10/1969 Bartlett ..252/357 72 Inventors: Gerd Rossmy; Gotz Koerner, both f 3,475,333 10/1969 Meldrum et al. ..252/3 Germany Primary Examiner-John T. Goolkasian [73] Assignee: Th. Goldschmidt A.G., Essen, Germany Assistant E i 1) ],F -i h [22] Filed, Oct 31 1969 Attorney-McGlew and Toren [2i] Appl. No.: 873,130 [57] ABSTRACT A water containing fire extinguishing foam concentrate com- [30] Foreign Application Priority Data prises an active ingredient about 1% to 10% by weight of a d f alf l Dec.4, 1968 Germany ..P 18 12 531.0 thegener CF23 F14 [52] U.S. Cl ..252/3, 252/8.05, 252/307,

260/448.2 N, 260/448.2 R, 260/561 HL F(CFCF2O),,CFCONXY [51] Int. Cl. ..A62d l/00 [58] Field of Search ..252/3, 8.05, 307, 353,357; wherein a is a number of between one and three inclusive, 260/561 HL, 448.2 N, 448.8 R X is hydrogen or Y and Y is a hydrophilating group such as polyethyleneglykol or an aminoxyd or ammoniumsalt con- [56] References Cited taining group.

The concentrate may also contain solubilizing agents. UNITED STATES PATENTS Ahlbrecht ..260/561 X 7 Claims, No Drawings FIELD OF INVENTION The invention relates to fire extinguishing foam concentrates which contain water and an organic fluor compound.

BACKGROUND INFORMATION AND PRIOR ART As is generally known, fires, particularly fires of fuels and propellants, are combatted by spraying foam in the form of continuous coats or coverings. Such foam blankets are also suitable for preventing the initial formation of fires.

Suitable prior art foaming agents for such purposes are prepared from protein salts, as for example from keratins, albumins, seed flour and the like which are modified by hydrolysis and stabilized with certain preselected metal salts.

However, as is wellknown in the art, foaming agents produced from protein hydrolysates cannot successfully be used for the combatting of certain types of fires. Thus, for example, such foaming agents are not suitable for fighting fuel fires or fires of polar substances as, for example, alcohol fires.

A further drawback of these known foaming agents resides in the fact that they are incompatible with dry fire extinguishing powders which are customarily used simultaneously, particularly if the powders have silicon containing surfaces. If such prior art foaming agents are used in conjunction with dry fire extinguishing powders, the foam has a tendency to collapse.

It has recently been suggested to employ foaming agents which are water soluble, ion-active derivatives of a fluorocarbonor a fluorosulfonic acid. Such compounds are usually applied in the form of an aqueous master solution. Concentrates of this kind have been described, for example, in German Pat. No. 1,2 16,1 16. However, also the latter type of prior art foaming agents is not fully satisfactory.

Thus, for example, the prior art fluorocarbon-tensides do not readily form stable aqueous foams of high expansion rate.

Accordingly, it is an object of the present invention to provide a foaming agent or concentrate of the indicated kind which has superior expansion rate properties as compared to the prior art compounds and which forms stable, aqueous foams.

Generally it is an object of this invention to improve on the art of fire extinguishing foam concentrates as presently practiced.

SUMMARY OF THE INVENTION In accordance with this invention it has suprisingly been found that another class of organic fluor compounds than that disclosed in German Pat. No. 1,216,116 exhibits particularly favorable operational characteristics when used as the active ingredient in fire extinguishing foams and that the above objects are fully attained with such other organic fluor compounds and that such other organic fluor compounds are superior in respect to-their fire combatting properties if compared with the known compounds.

The inventive fire extinguishing foam concentrate is characterized in that it comprises about 1 to by weight of compounds of the general formula wherein a is a number having the value of from one to three inclusive X is hydrogen or Y and Y stands for a hydrophilating group, particularly polyethyleneglykol or a group containing an aminoxyd or ammoniumsalt group. The concentrate may advantageously contain a sufficient amount of a solubilizing agent in order to render the concentrate water soluble.

The particularly favorable operational characteristics of the inventive fire extinguishing foam concentrate are primarily caused by the hydrophobic moiety of the active substances contained in the concentrate. The solubilizing group is accordingly of lesser importance. Some of the compounds embraced by the above general formula have proved to be particularly effective for the inventive purposes. Accordingly, fire extinguishing foam concentrates are particularly preferred wherein the active ingredient corresponds to a compound having the general formula L9 E 2 dH wherein c and d each have a value of from 0 to 50, while the sumofc+d= l to 50.

It is desirable but not necessary that the fluororganic compounds contained in the concentrate are water soluble. In the event that they are soluble with difficulty only or are substantially insoluble, they may be converted into water miscible form by the addition of a solubilizing agent of a nature known per se. Various solubilizing agents may be used for this purpose. Thus, for example, triethanolammoniumlaurylsulfate, triethanolammonium dodecylbenzenesulfonate as well as the various ionogenic and nonionogenic tensides with HLB values above 12 are suitable for the indicated purpose.

The operational characteristics of the fluoro compounds used in the inventive fire extinguishing foam concentrate may in some instances be favorably influenced by by the addition of preselected solubilizing agents. For this purpose the addition of water soluble polysiloxanes has proved to be particularly favorable. Such water soluble polysiloxanes, acting as solubilizing agents for the inventive purposes, are, for example, polysiloxane-polyalkyleneglykol-mixed block-copolymers as well as polysiloxanes which contain ionogenic groups linked to SiC, for example, organofunctional sulfates of polysiloxanes as disclosed, for example, in German Pat. No. 1,179,937.

Experiments have indicated that solubilizing agents of the following formula are particularly suitable Within a compound mixture, up to 50 mole of trimethylsilyl may be replaced by alkyl, preferably lower alkyl.

R is aryl or alkyl.

' If R stands for aryl, then phenyl is the preferred aryl group.

By contrast, if R is alkyl, the preferred alkyl group is methyl. Another preferred alkyl group is tri-yyy-trifluoropropyl.

The meaning of the symbol R may be different within the same siloxane group. For example, in addition to the preferred methyl groups, some phenyl groups or trifluoropropyl groups may be present. The group R, moreover, may be trimethylsiloxy.

n stands for zero or one.

If n l,"then the organosilicon compound is comprised of a sulfate group which is linked to the siloxane group through a carbon bridge. However, if n 0 then the organosilicon compound is a sulfonate.

m has a value of from one to three, preferably one to 1.3.

1 and r indicate the number of ethylenoxide units in the amine and have a value of from to seven. The sum of p, q and r is one through 20. Such compounds may be produced, for example, according to the process disclosed in German Patent 1,179,937.

sea water to form stable, firecombatting foams. This is an important advantage particularly considering the fact that the presently available fiuorocarbontensides cannot be foamed with sea water.

Also suitable as solubilizing agents are nonionogenic siloxanetensides of the following general formula E II In this formula the symbols R, R and m have the same meaning as indicated above.

R is hydrogen, alkyl or aryl. If R is aryl then phenyl is the preferred group; if R is alkyl, lower alkyl is preferred.

M stands for In the latter group, I has a value of from one to three.

u has a value offrom seven through 30.

The above organosilicon solubilizing agents have the par ticular advantage that they contribute not only to the solu' bilization but also significantly contribute to the formation of an effective fire extinguishing foam proper.

The advantageous operational characteristics of the inventive fire extinguishing foam concentrates will become clearly 10 apparent in considering and evaluating the following examples.

In order to test the expansion rate and foam stability the socalled foam impact test was used. A detailed description ofthe impact foam test is contained. for example. in the book by E. Manegold: Schaum. Strassenbau, Chemie und Technik-verlagsgesellschaft m.b.H., Heidelberg, 1953, pages 97 and 98. In performing the test, a measuring cylinder with a diameter of 5.4 cm. was used. The disc, used for the impact foam test, had a diameter of 5 cm. and contained 87 holes with a diameter of 1 mm. for each hole, The material to be foamed was filled into the measuring cylinder to a level of 3 cm. and was thereafter foamed by moving the disc up and down for times. The results which were obtained are tabulated in the following Tables Ia Ic.

The abbreviation HVT in the Table stands for half value time and indicates the time period which passed until an amount of liquid had been reformed which corresponded to one half of the original amount. The height of the foam was measured in millimeters.

The foam which was produced according to this foam impact method in tap water of about 10 German hardness was also used for extinguishing gasoline, supergasoline and butanol fires. For this purpose ccm. of these liquids were in 2) each case fed to a pot of 14.5 cm. diameter. The liquids were or the group then ignited and after a burning time of 2 minutes the extinguishing or fire combatting procedure was initiated. The U T results are tabulated in Tables Ila l to Ila 3, [lb 1 to 11b 3 and CH3 He 1 to He 3.

TABLE Ia.IMPACT FOAM TEST Distilled water Sea water Foam Foam height height Concentrate HVT in mm. l-IVT in mm.

Fluoroearbon concentrate as commercially available in 5% coneentration 5'26 150 2" 50 Fluorocarbon concentrate as commercially available in 3% concentration". 2'41 No loam CF CF; No loam No foam I F (C F-C F1-O )z-C F-CONH(CHz) I LI(CHa)2 0 F3 (3 F F(CFC F2O)g-C I CONH(CHz)aIII(CH-3) 0.2% and 7'67" 285 3'01" Si(CHa)a TABLE Ib.IMPAO'I FOAM TEST Distilled water Sea water Foam Foam height height Concentrate HVT in mm. HVT in mm.

0 Fa 0 F3 1 (J) F-C F2O)2 F-C ONH(CH1):1I}I(GH3)2 3'01" 165 No foam 0.2% and dodecylbenzenesulfonate of N[(CH2CH2 )1,4H]s

(I F :1 C F a F(CF-C F' O):CF-CONH(CH2)3N*(CH3)3I 6'59 210 Nofoum C F; 0 Fa F(( JF-CF2O)2CFOON(CH2CH2OH)2 N0 foam No foam TABLE Ic.-IMPACT FOAM TEST Distilled water Sea water Foam Foam height height Concentrate HV'I in mm. HVT in mm.

(IJF: i7 F(CFCF2O)zOF-OON(CHCH OH) 0.2% and 8'54" 300 3'40 150 (CH3) :1-Si0 Si0 CH;OHO)2.4H G9 Si(CHa)s (CHz)3OSOa HN-(CH11CH2O)2.1H

CHzCHzOhJ (13F: CF; F(CFCFO);OF-CON'(CH:CH OH)1 0.2% and dodecylbenzenesulfonate of 7'35 270 No foam TABLE IIa L FIRE EXTINGUISHIN'G TESTS Normal gasoline Extinguishing Amount (3:)

p53. 353233? "fiifiilififi? Concentrate I sion amounts of foam in 15 sec. Fluorocaxbonconeentrate as commercially available, 5% 1: 4 {38 I I} 5 Fluorocarbonconcentrate as commercially available, 3% 1:2 No foam CFz CF: F((EFCFa0)2-JF-CONH(CH2)aN(CHa)a No foam CF; CF; F(C JFCF2-O)2CF-CONH(CH2)3N(CH 5 02% and 1:9 33311 0.97

(CHa):1-Si0 -Sl0 CHzCH20)2.4H Sl(CHa)3 'llw vnlllu I111 11 Ill almond uxllnollnn M11111 \1'1114 vih'npoluhnl whore novvsaury.

TABLE IIa 2.FIRE EXTINGUISHING TESTS Normal gasoline Extinguishing time with Amount (g.) of Exdifferent concentrate for panamounts of extinction in Concentrate sion foam 15 sec.

0 Fa C F; i" (A) F-(i FzO)2-JJ F-C ONH(CH2)a(CHa)2 0.27 and 3B0 ml.=19"..... dodgcylbenzenesuifonate of {420 ml.=17".....} N[(CH2CH2O)2.4H]3

(1F; CF; 320m1.=17"-.... A (]J {42o ml.=14".....}

F-C F2-0)2- FC ONH(CH2)aN+(CHa)aI' D I a CFa No foam F (C F-C F2-O)z-$ F-C 0N(CH:CH2OH)1 The value for a 15 second extinction time was extrapolated where necessary.

TABLE IIe 3.FIRE EXTIN GUISHING TESTS Normal gasoline Extinguishing Amount (g.) Extime with diioi concentrate panferent amounts for extinction Concentrate sion of foam in 15 sec.

II {3$i1i? II 116 F (C FC Fr-O )2C F-O 0N(CH,CH OH)1 0.2% and (CHa):Si0 Si0 (CHzCHzO)2.4H 6B SKCHa):

(CH2)a-O-S 03 HN 0H,0H,0 )I.4H

(CHzC 2 )IAH CF OF 420ml.=25

3 a {530ml.=15 F (C FCFzO)z-C FCON(CH;CH,0H)1

0.2% and dodecylbenzenesulfonate of 2CH2 )2.4H]a

The value for a 15 second extinction time was extrapolated were necessary.

TABLE 11b 1.FIRE EXTIN GUISHIN G TESTS Super gasoline Extinguishing Amount (g.) Extime with diiof concentrate pani'ercnt amounts for extinction Concentrate sion of ioam in 16 sec.

Flnorocarbonconccntratc as commercially available in 5% concentration i 1: 4 I I} 4. 4 Fluorocai'bonconccntratc as commercially available in 3% concentration 1:2 No foam OF; CF; Noioam F (C F-C Fz-Oh-C FOONH(CHn)aN(CH3)1 assesses} F (C F-C Fz-O)g-C FCONH(CHa)aN(CH3)a 0.2% and (CH3)3S1O -Si0 (CHzCHzmuH 6B Si(CH3)3 (CH2)30'S 03 HN-(CIIgCH OMAII ((Hlafllhflhfll 'Iho vnlnn [m u If: sovmul mllm'ilnll Hm" woe mlrupulnlmi worn um-nssuly TABLE IIb 2.-FIRE EXTINGUISHIN G TESTS Super gasoline Extinguishing Amount (g.) Extime with of concentrate pandifierent for extinction Concentrate sion amounts of foam in 15 sec.

CFa CF; 42om1.=22" g 1 {460m1.=16 F( F-C F-O)2-- F-C 0NH(CH1);II(CH@)2 0.2% and dodecylbenzenesulfonate of N((CH2CHzO)2.4H]a

CF; CF; 320m1.=18" (E J a) e {aeum1.=1e" F( F-C Fz0) FOONH(CH):N (CHmI CFa CFa No foam F (27 F-C F2-O)2([3 F-C ON(CH2CH2OH)2 'Ifhe value for a 15 second extinction time was extrapolated were necessary. i M A TABLE Ilb 3.FIRE EXTINGUISHIN G TESTS Super gasoline Extinguishing Amount (g.)

Extime with ditoi concentrate panferent amounts for extinction The value for a 15 second extinction time was extrapolated were necessary.

TABLE I10 1.FIRE EXTINGUISHING TESTS n-Butanol Extinguishing Amount (g.) Extime with difof concentrate panierent amounts for extinction Concentrate sion of foam in 15 sec.

Fluorocarbonconcentrate as commercially available, 5% 1 4 fiI t I LI} 2. 7 Fluorocarbonconcentrate as commercially available, 3% e. 1: 2 1 1 333531: CF; CF; Nofoam F(( 1F-O Fn-O )a-C F-G ONH(CHz)sN(CHa)n {itfifiiii' ij} F (CF-CF2-O)nCF-CONH(CHz)aN(OHa)z 0.2% and (OHM-S10 Si0 CH2CHIO L4H G3 Si(CHa)a Hoke-s1 03 HN-(CH,CHnO)n.4H

GIIQOI'IIO)3JH Ste w elbeeea de w i sesiteeeleteewer newswa 7 f5 TABLE lIe 2.-FIRE EX'IIN GUISHIN G TESTS n-Butanol Extinguishing time with Amount (gfi) Exdifierent of concentrate panamounts of for extinction Concentrate sion foam in 15 sec.

C F: C Fa i (C1"-C 1 2-O)2C F-C ONI-I(CHz)aN(CH:)z

I 210 ml.=fi 1:5 80ml.=9 1.02

0.2% and dodecylbenzenesulfonate of N[(CH2OH2O)2,4H]3

CF; 01'; 210 ml.=4... I (I: a) 9 1:6 105 ml.=5" 0.036 F(g;CF2-O)2- FCONH(CH2)aN (0mm 90ml.=(

C F3 0 F 3 Ff-0 F2O)2JJ FCON(GH2CH2OH)2 No foam 1 Fire is not extinguished. The value for a 15 second extinction time was extrapolated were necessary. 5 *No ccprresponding value could be extrapolated. The amount of concentrate is calculated for extinction time of secon 5.

TABLE I 3.-FIRE EXTINGUISHING TESTS n-Butanol Extinguishing Amount of Extime with concentrate of pandifferent extinction Concentrate sion amounts of foam in see.

CF; CF 210 ml.=6"

1-10 0.46 g. F (C F-C Fg-O)z0 F-CON(OH:CH;OH)1

0.2% and (EH: (CHa)aSi-O s1-o omoHmmH SKCHS);

(ormro s 03 HN-(CH CHzOhdI (CH:CH2O)7.4H

CF3 CF; 210 ml.=5"

1:9 180 ml.=10" 0.51 g.+ F(CFC F2-O)2CF-CON(CHaCHaOH)a ml.=(

0.2% and dodecylbenzenesulfonate oi NLgQHncHgo )2.4H]

1 Fire is not extinguished.

The value for a 15 second extinction time was extrapolated were necessary. +No corresponding value could be extrapolated. The amount of concentrate is calculated for extinction time of 5 seconds.

What is claimed is:

1. In a fire extinguishing water containing foam concentrate, the improvement which comprises that its active ingredient is about I to 10% by weight of a compound of the formula wherein,

a is a number having a value of from one to three inclusive,

X is hydrogen or Y and Y is a hydrophilating group; said concentrate additionally containing a solubilizing agent in an amount sufficient to render the concentrate water soluble, said solubilizing agent having an hlb value above 12.

2. The improvement of claim 1, wherein said solubilizing agent is triethanol ammonium laurylsulfate, triethanol ammonium dodecyl benzene sulfonate, an ionogenic tenside or a non-ionogenic tenside.

3. The improvement as claimed in claim 1, wherein the hydrophilating group Y is polyethyleneglyko] or a group containing aminoxide or ammoniumsalt.

4. The improvement as claimed in claim 1, wherein the active ingredient corresponds to the formula wherein b 2 or 3.

5. The improvement as claimed in claim 1, wherein the active ingredient is a compound of the general formula (CHs)a S i0 Si(CHa)a said agent being contained in the concentrate in an amount by weight corresponding to three to 15 times the quantity of said active ingredient. 

2. The improvement of claim 1, wherein said solubilizing agent is triethanol ammonium laurylsulfate, triethanol ammonium dodecyl benzene sulfonate, an ionogenic tenside or a non-ionogenic tenside.
 3. The improvement as claimed in claim 1, wherein the hydrophilating group Y is polyethyleneglykol or a group containing aminoxide or ammoniumsalt.
 4. The improvement as claimed in claim 1, wherein the active ingredient corresponds to the formula wherein b 2 or
 3. 5. The improvement as claimed in claim 1, wherein the active ingredient is a compound of the general formula wherein b 2 or 3 and c and d are each numbers having a value of from to 50, the sum of c + d 1 to
 50. 6. The improvement as claimed in claim 1, wherein the solubilizing agent is a water soluble polysiloxane.
 7. The improvement as claimed in claim 6, wherein the polysiloxane is a compound of the formula 